EP2104707A1 - Kautschukzusammensetzung, enthaltend eine polymaleinimidverbindung - Google Patents

Kautschukzusammensetzung, enthaltend eine polymaleinimidverbindung

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Publication number
EP2104707A1
EP2104707A1 EP07856873A EP07856873A EP2104707A1 EP 2104707 A1 EP2104707 A1 EP 2104707A1 EP 07856873 A EP07856873 A EP 07856873A EP 07856873 A EP07856873 A EP 07856873A EP 2104707 A1 EP2104707 A1 EP 2104707A1
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EP
European Patent Office
Prior art keywords
composition
composition according
polymaleimide
phr
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP07856873A
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English (en)
French (fr)
Inventor
Christiane Blanchard
Mathieu Manceau
Salvatore Pagano
Vanessa Roy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Compagnie Generale des Etablissements Michelin SCA
Michelin Recherche et Technique SA France
Original Assignee
Michelin Recherche et Technique SA Switzerland
Michelin Recherche et Technique SA France
Societe de Technologie Michelin SAS
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Application filed by Michelin Recherche et Technique SA Switzerland, Michelin Recherche et Technique SA France, Societe de Technologie Michelin SAS filed Critical Michelin Recherche et Technique SA Switzerland
Publication of EP2104707A1 publication Critical patent/EP2104707A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition

Definitions

  • the present invention relates to rubber compositions intended in particular for the manufacture of tires or semi-finished products for tires, as well as antireversion agents that can be used for the thermal protection of such compositions.
  • the known disadvantage of sulfur vulcanization is that it leads to a limited resistance of the vulcanizates obtained, due to thermal aging ("thermal aging") of the latter.
  • thermal aging the vulcanizates of diene elastomers crosslinked from sulfur have a significant sensitivity to temperature when the latter reaches a value close to the initial firing temperature or vulcanization.
  • This phenomenon known as reversion, is accompanied by a degradation of the mechanical properties of the vulcanizates.
  • antireversion agents for thermally stabilizing the vulcanizates.
  • a widely described family of anti-eversion agents is the maleimide compounds, more particularly the bismaleimides or biscitraconimides used alone or in combination with other compounds (see for example EP 191931 or US 4803250, EP 640114 or WO93 / 23467, EP 703943 or US 5872188, EP 709234 or US 5503940, EP 823453 or US 6079468, EP 988999, US 5328636, US 5616279, US 5623007, WO92 / 07904 or US 5426155, WO95 / 16738, JP2001 -226528).
  • maleimide compounds make it possible to offer the vulcanizates an improved resistance to reversion compared with the aforementioned bismaleimides or biscitraconimides.
  • These maleimide compounds are citraconimidomaleimides (WO 2005/026250) and itaconimidomaleimides (WO 2006/099985) which in both cases have a maleimide function associated with a citraconimide function for one and itaconimide for the others.
  • a first subject of the invention relates to a rubber composition that can be used for the manufacture of tires, based on at least one diene elastomer, a reinforcing filler, a sulfur-based vulcanization system and a maleimide compound, characterized in that said maleimide compound is a polymaleimide of the formula:
  • the invention also relates to a method for preparing a rubber composition that can be used for the manufacture of tires and having an improved resistance to reversion, this composition being based on a diene elastomer, a reinforcing filler and a sulfur-based vulcanization system, said method comprising the following steps:
  • the invention also relates to the use of a composition according to the invention for the manufacture of a finished article or a semi-finished rubber product intended for any system of ground connection of motor vehicles, such as pneumatic, internal safety support for tire, wheel, rubber spring, elastomeric joint, other suspension and anti-vibration element.
  • motor vehicles such as pneumatic, internal safety support for tire, wheel, rubber spring, elastomeric joint, other suspension and anti-vibration element.
  • the subject of the invention is particularly the use of a composition according to the invention for the manufacture of tires or semi-finished rubber products intended for these tires, these semi-finished products being preferably chosen from the group consisting of treads, crown reinforcement plies, flanks, carcass reinforcement plies, beads, protectors, layers, rubber blocks and other internal rubbers, in particular decoupling erasers, intended to provide the connection or the interface between the aforementioned zones of the tires.
  • the invention also relates to finished articles and semi-finished products of rubber themselves, in particular tires and semi-finished products for tires, when they comprise an elastomeric composition according to the invention.
  • the tires in accordance with the invention are intended in particular for passenger vehicles as well as for industrial vehicles chosen from vans, "heavy goods vehicles” - ie, metro, buses, road transport vehicles (trucks, tractors, trailers), off-road vehicles. la-route - agricultural or civil engineering machinery, airplanes, other transport or handling vehicles.
  • the rubber compositions are characterized, before and after firing, as indicated below.
  • the measurements are carried out at 130 ° C. in accordance with the French standard NF T 43-005 (1991).
  • the evolution of the consistometric index as a function of time makes it possible to determine the toasting time of the rubber compositions, evaluated according to the above-mentioned standard by the parameter T5 (case of a large rotor), expressed in minutes, and defined as the time required to obtain an increase in the consistometric index (expressed in MU) of 5 units above the minimum value measured for this index.
  • the measurements are carried out at 150 ° C. with an oscillating chamber rheometer according to DIN 53529 - Part 3 (June 1983).
  • the evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization reaction.
  • the measurements are processed according to DIN 53529 - Part 2 (March 1983): the minimum and maximum torques, measured in dN.m (deciNewton.meter), are respectively named C m j n and C max ; the difference noted ⁇ Couple (in dN.m) between C max and C m j n is also measured, which makes it possible to evaluate the vulcanization efficiency.
  • the mechanical properties indicated below are those measured at "optimum cooking", that is to say, in known manner, those obtained for a determined cooking temperature, after the minimum cooking time to reach the maximum rheometric torque C max .
  • the reversion can be analyzed according to different methods, the aim being to determine, indirectly, the evolution of the density of bridges of sulfur, between a so-called optimum cooking (corresponding to maximum torque C max ) and prolonged cooking.
  • the first approach consists of measuring the evolution (decrease) of the rheometric torque: the parameters AR 60 and AR 180 represent the evolution in% of the torque between C max and the torque measured after 60 or 180 min of cooking, respectively, at a determined firing temperature (eg 150 ° C). The higher the AR 60 and ARi 80 parameters, the greater the reversion phenomenon.
  • the second approach is to measure the evolution (decrease) of the aforementioned MA100 or MA300 modules: the parameters ⁇ MA100 and ⁇ MA300 correspond to the evolution in% of the respective modules measured at the optimum of cooking (C max ) and after a cooking of 6 hours, at a determined cooking temperature (150 ° C).
  • C max the optimum of cooking
  • 150 ° C the cooking temperature
  • the rubber compositions according to the invention are based on at least one (that is to say one or more) diene (s) elastomer (s), one (or more) reinforcing filler (s) (s). ), one (or more) crosslinking system (s) and one (or more) polymaleimide compound (s) of formula (I) above.
  • composition based on means a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended to react with each other. at least in part during the various phases of manufacture of the composition, in particular during its vulcanization.
  • elastomer or “diene” rubber is meant in known manner an elastomer derived at least in part (ie a homopolymer or a copolymer) of monomers dienes (monomers bearing two carbon-carbon double bonds, conjugated or not). These diene elastomers can be classified into two categories: "essentially unsaturated” or "essentially saturated”.
  • essentially unsaturated is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%).
  • diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated” diene elastomers. "(low or very low diene origin, always less than 15%).
  • the term “highly unsaturated” diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
  • iene elastomer can more particularly be understood as being capable of being used in the compositions in accordance with the invention:
  • diene elastomer any type of diene elastomer, one skilled in the art of the tire will understand that the present invention is first used with essentially unsaturated diene elastomers, in particular of the type (a) or ( b) above.
  • conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5 alkyl) -1,3-butadienes, such as for example 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1 3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
  • Suitable vinyl aromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tertiarybutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene and divinylbenzene. vinyl naphthalene.
  • the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinyl aromatic units.
  • the elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used.
  • the elastomers can be for example block, statistical, sequence, microsequential, and be prepared in dispersion or in solution; they can be coupled and / or star or functionalized with a coupling agent and / or starring or functionalization.
  • butadiene-styrene-isoprene copolymers are especially suitable those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60%.
  • the diene elastomer of the composition according to the invention is preferably chosen from the group of highly unsaturated diene elastomers which consists of polybutadienes (BR), polyisoprenes (IR), natural rubber (NR) 5 copolymers butadiene, isoprene copolymers and mixtures of these elastomers.
  • Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-copolymers.
  • SBIR butadiene-styrene
  • the diene elastomer is predominantly (that is to say for more than 50 phr) an SBR, whether it is an SBR prepared in emulsion ("ESBR") or a solution-prepared SBR ("SSBR”), or a blend (mixture) SBR / BR, SBR / NR (or SBR / IR), or BR / NR (or BR / IR).
  • SBR SBR prepared in emulsion
  • SSBR solution-prepared SBR
  • an SBR elastomer use is made in particular of an SBR having a styrene content of between 20% and 30% by weight, a vinyl bond content of the butadiene part of between 15% and 65%, a bond content of trans-1,4 of between 15% and 75% and a Tg of -20 ° C to -55 ° C; such an SBR can be advantageously used in admixture with a BR preferably having more than 90% cis-1,4 bonds.
  • the diene elastomer is predominantly (for more than 50 phr) an isoprene elastomer.
  • the compositions of the invention are intended to constitute, in tires, the rubber matrices of certain treads (for example for industrial vehicles), crown reinforcing plies (for example work webs, protective webs or hoop webs), carcass reinforcement plies, flanks, beads, protectors, underlayments, rubber blocks and other internal gums providing the interface between aforementioned areas of the tires.
  • compositions according to the invention are for example advantageously usable as "decoupling gums" in the areas of the tire (called “decoupling zones”) whose function is to ensure a mechanical decoupling between two different parts of said tire, these zones being of known way exposed to the risks of heating, and therefore reversion most important. They can also advantageously form the annular gum profiles used to stiffen the sidewalls of tires designed for run-flat tires (see US Patent No. 5,427,166, for example).
  • isoprene elastomer in known manner a homopolymer or a copolymer of isoprene, in other words a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), different isoprene copolymers and mixtures of these elastomers.
  • NR natural rubber
  • IR synthetic polyisoprenes
  • isoprene copolymers examples include isobutene-isoprene copolymers (butyl rubber-HR), isoprene-styrene copolymers (SIR), isoprene-butadiene copolymers (BIR) or isoprene-butadiene-styrene copolymers. (SBIR).
  • This isoprene elastomer is preferably natural rubber or synthetic cis-1,4 polyisoprene; of these synthetic polyisoprenes, polyisoprenes having a content (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used.
  • the composition conforms to The invention may contain at least one essentially saturated diene elastomer, in particular at least one EPDM copolymer or a butyl rubber (optionally chlorinated or brominated), whether these copolymers are used alone or in a mixture with diene elastomers which are highly unsaturated as mentioned above, in particular NR or IR, BR or SBR.
  • compositions of the invention may contain a single diene elastomer or a mixture of several diene elastomers, the diene elastomer (s) may be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers.
  • reinforcing filler known for its capacity to reinforce a rubber composition that can be used for manufacturing tires, for example an organic filler such as carbon black, or a reinforcing inorganic filler such as silica to which will be associated in this second case a coupling agent.
  • Carbon blacks are suitable for all carbon blacks, in particular blacks of the HAF, ISAF, SAF type conventionally used in tires (so-called pneumatic grade blacks).
  • the reinforcing carbon blacks of the 100, 200 or 300 series such as, for example, black NI 15, N134, N234, N326, N330, N339, N347, N375, or, depending on the intended applications, black higher series (eg N660, N683, N772).
  • any inorganic or mineral filler regardless of its color and origin (natural or synthetic), also called “white” charge, “clear” charge or “non-black filler” charge as opposed to carbon black, this inorganic filler being able to reinforce on its own, with no other means than an intermediate coupling agent, a rubber composition intended for the tire manufacturing, in other words able to replace, in its reinforcing function, a conventional carbon black pneumatic grade; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
  • -OH hydroxyl groups
  • Suitable reinforcing inorganic fillers are mineral fillers of the siliceous type, in particular silica (SiO 2 ), or of the aluminous type, in particular alumina (Al 2 O 3).
  • the silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface area both less than 450 mVg, preferably from 30 to 400 m 2 / g .
  • HDS highly dispersible precipitated silicas
  • reinforcing aluminas examples include “Baikalox”"A125” or “CR125” aluminums from the Baikowski company, “APA-100RDX” from Condea, “Aluminoxid C” from Degussa) or “AKP-G015" from Sumitomo Chemicals.
  • a well-known at least bifunctional coupling agent (or bonding agent) will be used in a well known manner to provide a sufficient chemical and / or physical connection between the inorganic filler. (surface of its particles) and the diene elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
  • the content of total reinforcing filler is between 10 and 200 phr, more preferably between 20 and 150 phr (parts by weight per hundred parts of elastomer), optimum being different depending on the intended applications: the level of reinforcement expected on a bicycle tire, for example, is known in a manner well below that required on a tire capable of running at high speed in a sustained manner, for example a motorcycle tire, a tire for a passenger vehicle or for a commercial vehicle such as a heavy truck.
  • the rubber compositions of the invention have the novel and inventive characteristic of using, as anti-eversion agent, a polymaleimide compound comprising at least three maleimide functions, corresponding to the following formula (I):
  • the radicals R 1, R 2 , R 3 and R 4 comprise from 1 to 25 carbon atoms and optionally one or more heteroatoms chosen from O, N, S, Si and P.
  • the radicals R 1, R 2 , R 3 and R 4 are chosen from the group consisting of alkylenes having from 1 to 20 carbon atoms, cycloalkylenes having from 6 to 24 carbon atoms, arylenes having from 6 to 18 carbon atoms and aralkylenes having 7 to 25 carbon atoms, the alkylene radicals being branched and may be interrupted by one or more heteroatoms selected from O, N, S, Si and P.
  • the radicals R 1, R 2 and R 3 are alkylenes and n is 0, X being then a nitrogen atom.
  • radicals R 1, R 2 and R 3 are ethylenes, the selected polymaleimide being even more preferably tris (2-maleimidoethyl) amine.
  • the polymaleimide of formula (I) is present in the composition according to the invention at a preferential rate of between 0.1 and 10 phr. Below the minimum indicated, the intended technical effect may be insufficient, whereas beyond the maximum indicated, there is a double risk for the plasticizing compositions in the raw state and excessive stiffening at the same time. cooked state. For all these reasons, a more preferred level is used in a range of 0.2 to 5 phr. An amount within a range of 0.2 to 3 phr has proved particularly suitable for pneumatic application.
  • the vulcanization system itself is based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.
  • sulfur or a sulfur-donor agent
  • a primary vulcanization accelerator To this basic vulcanization system are added, incorporated during the first non-productive phase and / or during the production phase as described later, various known secondary accelerators or vulcanization activators such as zinc oxide.
  • Sulfur is used at a preferential level of between 0.5 and 10 phr, more preferably between 1 and 8 phr, in particular between 1 and 6 phr, when the composition of the invention is intended, according to a preferred embodiment of the invention. invention, to constitute an inner tire rubber, in particular a decoupling rubber.
  • the primary vulcanization accelerator is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr.
  • Such an accelerator it is known, must allow a crosslinking of the rubber compositions in industrially acceptable times, while preserving a minimum safety period ("toasting time") during which the compositions can be shaped without risk of premature vulcanization (“roasting").
  • Any compound capable of acting as an accelerator for vulcanizing diene elastomers in the presence of sulfur may be used.
  • Thiazole accelerators and their derivatives are especially selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzothiazyl disulfide, N-cyclohexyl-2-benzothiazyl sulfenamide, N, N-dicyclohexyl-2-benzothiazyl sulfenamide, N 4-tert-butyl-2-benzothiazylsulfenamide, N-cyclohexyl-2-benzothiazylsulfenimide, N-tert-butyl-2-benzothiazylsulfenimide and mixtures thereof.
  • Thiuram type accelerators are especially chosen from the preferred group consisting of tetramethyl-thiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetraisoisobutyl disulfide.
  • thiazole or thiuram type accelerators are described in more detail, in particular in the patent application WO 2005/026250 already mentioned above.
  • accelerators that can be used in the compositions of the invention, mention may be made of zinc dithiocarbamates, in particular zinc tetramethyl dithiocarbamate, zinc tetraethyl dithiocarbamate and zinc tetrabenzyl dithiocarbamate. Among them, zinc tetrabenzyl dithiocarbamate is more preferably retained.
  • the primary vulcanization accelerators used in the composition according to the invention are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (in abbreviated “CBS”), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (abbreviated “DCBS”), N-tert-butyl-2-benzothiazyl sulfenamide (abbreviated as "TBBS”), N-tert-butyl- 2-benzothiazyl sulfenimide (abbreviated as "TBSI”) and mixtures of these compounds.
  • MBTS 2-mercaptobenzothiazyl disulfide
  • CBS N-cyclohexyl-2-benzothiazyl sulfenamide
  • DCBS N-dicyclohexyl-2-benz
  • the elastomeric compositions according to the invention may also comprise all or part of the usual additives used in rubber compositions intended for the manufacture of a tire, such as, for example, plasticizers or extension oils, that these are aromatic or non-aromatic nature, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents, adhesion promoters, coupling activators, reinforcing resins, acceptors and / or donors of methylene, or even other anti-eversion agents, for example conventional bismaleimides or biscitraconimides.
  • plasticizers or extension oils that these are aromatic or non-aromatic nature, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents, adhesion promoters, coupling activators, reinforcing resins, acceptors and / or donors of methylene, or even other anti-eversion agents, for example conventional bismaleimides or bisc
  • these compositions comprise, as preferred non-aromatic or very weakly aromatic plasticizing agent, at least one compound selected from the group consisting of naphthenic, paraffinic, MES, TDAE oils, esters (especially trioleate) oils.
  • glycerol the hydrocarbon plasticizing resins preferably having a high value of Tg (preferably greater than 30 ° C), and mixtures of such compounds.
  • the reinforcing filler used is an inorganic filler
  • recovery agents for such an inorganic filler more generally, processing aid agents that are capable in a known manner, thanks to an improvement in the dispersion of the inorganic filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to implement in the green state.
  • compositions are manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (so-called “non-productive” phase) at high temperature, up to a maximum of maximum temperature between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, followed by a second phase of mechanical work (so-called “productive” phase) to a lower temperature, typically less than 1 10 ° C, for example between 40 ° C and 100 ° C, finishing phase during which is incorporated the vulcanization system.
  • a first phase of work or thermomechanical mixing at high temperature, up to a maximum of maximum temperature between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C
  • a second phase of mechanical work so-called “productive” phase
  • the method according to the invention for preparing a rubber composition having improved resistance to reversion comprises the following steps: . to incorporate in a diene elastomer, during a first so-called “non-productive" step, at least one reinforcing filler, by thermomechanically kneading the whole, in one or more times, until a maximum temperature of between 10 ° C. C and 190 ° C; • cool the assembly to a temperature below 100 ° C;
  • the non-productive phase is carried out in a single thermomechanical step during which all the necessary basic constituents (diene elastomer) are introduced into a suitable mixer such as a conventional internal mixer. , reinforcing filler and coupling agent if necessary, optionally all or part of the polymaleimide compound), then in a second step, for example after one to two minutes of mixing, the other additives, any additional coating or processing agents, with the exception of the vulcanization system.
  • the total mixing time in this non-productive phase is preferably between 1 and 15 minutes.
  • the vulcanization system and the polymaleimide compound are then incorporated in an external mixer such as a roll mill. or the remaining part, if any).
  • the whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 minutes.
  • the final composition thus obtained can then be calendered, for example in the form of a sheet, a plate or extruded, for example to form a rubber profile used for the manufacture of a semi-finished tire product, such as webs, tapes, underlays, various rubber blocks, reinforced or not with textile or metal reinforcements, intended to form part of the tire structure.
  • the vulcanization (or baking) can then be carried out in a known manner at a temperature generally of between 130 ° C. and 200 ° C., preferably under pressure, for a sufficient time which may vary, for example, between 5 and 90 min in dependence. in particular the cooking temperature, the vulcanization system adopted and the kinetics of vulcanization of the composition under consideration.
  • the invention relates to the rubber compositions described above both in the so-called “raw” state (i.e., before firing) and in the so-called “cooked” or vulcanized state (i.e. after vulcanization).
  • the polymaleimide compound of formula (I) according to the invention used in the following examples is tris (2-maleimidoethyl) amine, a synthetic route of which is described by Gerhard Kossmehl, Hans-Ingo Nagel and Andreas Pahl in "Die Angewandte Makromoleculare Chemie, 227, 139-157 (1995).
  • an internal mixer is introduced with the usual "Banburry” type pallets (capacity: about 3.5 liters), 70% filled, and whose initial tank temperature is about 60 ° C., the diene elastomer (or the mixture of diene elastomers, if appropriate), the reinforcing filler (carbon black) and, after one to two minutes of mixing, the various other ingredients with the exception of vulcanization system and anti-eversion agent.
  • Thermomechanical work (non-productive phase) is then carried out in one step (total mixing time equal to about 5 minutes), until a maximum "falling" temperature of about 160 ° C. is reached.
  • the mixture thus obtained is recovered, cooled and then the vulcanization system is added and (if it is present in the composition) the anti-eversion agent on an external mixer (homo-finisher) at 40 ° C., mixing the whole. (productive phase) for 3 to 4 minutes on this roller tool.
  • compositions thus obtained are then calendered in the form of plates (thickness of 2 to 3 mm) or thin sheets of rubber for the measurement of their physical or mechanical properties, or extruded to form profiles that can be used directly, after cutting and / or assembly to the desired dimensions, as a semi-finished tire product.
  • This test aims to demonstrate the resistance to reversion and improved thermal stability of a composition according to the invention intended to form a decoupling rubber located between the crown reinforcement and the radial carcass reinforcement of a tire. of the civil engineering type.
  • composition according to the invention is compared with three control compositions, with or without an anti-eversion agent, the three compositions tested being identical, with the following differences:
  • composition T1 control without antireversion agent
  • T2 composition control with conventional anti-eversion agent (bismaleimide)
  • composition C1 composition according to the invention (trismaleimide).
  • the bismaleimide compound used in the control composition T2 is meta-phenylenebismaleimide (abbreviated to "MPBM”), which is well known to those skilled in the art and corresponds to the following particular formula:
  • MPBM meta-phenylenebismaleimide
  • the essential characteristic distinguishing the two compounds above, and therefore the composition according to the invention C1 of the control composition T2 is the presence of a third maleimide function without the presence of an aromatic ring between the different maleimide functions.
  • the two maleimide compounds (bismaleimide and trismaleimide) are used at an isomolar level relative to each other in their respective composition.
  • Table 1 gives the formulation of the different compositions (rate of the different products expressed in phr), and Table 2 gives the properties before and after curing, the rheometric properties as well as various parameters measuring the reversion.
  • the evolution of the rheometric torque is followed after 40 minutes at 150 ° C.
  • the thermal stability of the compositions is also assessed by the evolution of the nominal secant modulus at 100% and at 300% elongation, between the measurement at the optimum of cooking and after prolonged cooking for 6 hours (temperature of 150 ° C. ).

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EP07856873A 2006-12-27 2007-12-19 Kautschukzusammensetzung, enthaltend eine polymaleinimidverbindung Withdrawn EP2104707A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0611513A FR2910901B1 (fr) 2006-12-27 2006-12-27 Composition de caoutchouc comportant un compose polymaleimide
PCT/EP2007/011150 WO2008080553A1 (fr) 2006-12-27 2007-12-19 Composition de caoutchouc comportant un compose polymaleimide

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WO (1) WO2008080553A1 (de)

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EP2284217B1 (de) * 2009-08-07 2011-12-07 Rhein Chemie Rheinau GmbH Vulkanisationsbeschleunigende Mischung
WO2012044317A1 (en) * 2010-09-30 2012-04-05 Michelin Recherche Et Technique S.A. Barrier layer for inflatable articles
FR2975045B1 (fr) * 2011-05-12 2013-06-14 Michelin Soc Tech Pneumatique dont la zone sommet est pourvue d'une sous-couche comportant un elastomere thermoplastique
FR2975044B1 (fr) 2011-05-12 2013-06-14 Michelin Soc Tech Pneumatique pourvu d'une bande de roulement comprenant un elastomere thermoplastique
JP5986368B2 (ja) * 2011-11-16 2016-09-06 株式会社ブリヂストン 変性天然ゴム及びその製造方法、並びに、ゴム組成物及びタイヤ
FR3021971B1 (fr) 2014-06-05 2016-06-03 Michelin & Cie Pneumatique a faible resistance au roulement
FR3021972B1 (fr) 2014-06-05 2016-06-03 Michelin & Cie Pneumatique a faible resistance au roulement
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JP5450090B2 (ja) 2014-03-26
US8008399B2 (en) 2011-08-30
WO2008080553A1 (fr) 2008-07-10
US20100022699A1 (en) 2010-01-28
JP2010514859A (ja) 2010-05-06
FR2910901B1 (fr) 2010-06-25
FR2910901A1 (fr) 2008-07-04

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